CHM149/B41 Arceo, Chrissie A.

Exam 3 July 2, 2013

Partitioning equilibrium can be used to further illustrate how chemical structure controls chemical behaviour. By understanding the equilibrium partitioning, one can also understand of the molecular factors that govern partitioning processes involving bulk liquid organic phases. Lastly, understanding the equilibrium partitioning behaviour can also help in determining the different thermodynamic constants in a given system.

The equilibrium partition constant is defined by considering only one chemical species in each phase. This partition constant is related to the Gibbs free energy of transfer, 12Gi. The molecular factors that determine its magnitude in the case of (a) (b) (c) (d) Partitioning between the gas phase and a bulk liquid is adsorption. Partitioning between gas phase and the surface of a condensed phase is Partitioning between two bulk phases is Absorption is the partitioning between a bulk liquid and a solid surface.

(a) PCBs, methane, and CFCs. (b) Carboxylic acids, benzene, and methylbenzene. The three are H-acceptors (electron donors). (c) Methanol, ethylene glycol, and n-octanol.

T( ) 269 25

T(K) 569.15 298.15

P/atm 1 8.684x10-4

lnP* 0 -7.049

1/T 1.76x10-3 4.30x10-3

( ) ( )

( )( ( ) ( )

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(a) The aqueous solubility of a liquid compound changes with temperature is dictated by its excess enthalpy. (b) The aqueous solubility of a solid compound changes with temperature is dictated by the enthalpy of solution which is given by the sum of the enthalpy of fusion and the excess enthalpy in aqueous solution (c) The aqueous solubility of a gaseous compound changes with temperature is dictated by the enthalpy of solution is given by the sum of the enthalpy of condensation (also equal to the negative enthalpy of vaporization) and the excess enthalpy in aqueous solution. The thermodynamic quantities needed for quantifiying this temperature dependence are the enthalpy of solution, enthalpy of fusion, and the excess enthalpy in aqueous solution.

Dissolved salts, when high enough, significantly alter the air-water partitioning behaviour by increasing the interfacial partitioning coefficient. This salting-out effect is exponentially proportional with increasing salt concentration.

(a) To know which the affinity of the sorbate for the sorbent remains the same over the observed concentration range; (b) To know where the binding sites become filled and/or remaining sites are less attractive to the sorbate molecules; (c) To know where all sites are saturated and no more additional sorption is possible; (d) To know the superposition of several individual isotherms that are characteristic for each type of sorbent; and, (e) To know the effect of the previously sorbed molecules that lead to a modification of the sorbent that favors further sorption.

Sorption isotherms describe the equilibrium partitioning between the sorbed and desorbed phase. The types of sorption isotherms that may be encountered are Freundlich, which is an empirical description, and Langmuir, which is the sorption to a limited number of sites. The shape of a sorption isotherm alone does not prove which sorption mechanism it is operating because sorption can take place via many different mechanism combinations, but the shape must be consistent with the mechanism of sorption.